Method for hydrogenation of metathesis polymers

ABSTRACT

The present invention provides a method for hydrogenating a metathesis polymer solution obtained by polymerization in the presence of a metathesis polymerization catalyst comprising (a) the catalyst component of a transition metal compound and (b) the co-catalyst component of a metal compound by bringing the above solution into contact with hydrogen, without adding an inactivating agent for the metathesis polymerization catalyst, that is, with the solution left to contain the catalyst, in the presence of a hydrogenation catalyst comprising a transition metal compound (c) and a reductive metal compound (d) and if necessary by adding an acid-binding compound. According to this method, both addition of the inactivating agent and removal of the metathesis polymerization catalyst are not necessary, and also the hydrogenation can be carried out at a lower temperature and under a lower pressure than in hydrogenation with a supported-type catalyst, so that the efficiency of production of the hydrogenated product is excellent. Besides, even if tungsten hexachloride (WCl 6 ), etc. are used as the catalyst component, an effect of preventing a hydrogenation reactor from corrosion by a hydrogen halide, can be obtained.

This application is a continuation of application Ser. No. 08/282,596filed Jul. 29, 1994, now abandoned.

FIELD OF THE INVENTION AND RELATED ART STATEMENT

1. Field of the Invention

The present invention relates to a method for hydrogenation ofmetathesis polymers. More particularly, it relates to a method forhydrogenation of metathesis polymers in which the unsaturated bonds inthe main chain of the polymers are saturated with a good efficiency andunder mild conditions.

2. Related Art

The metathesis polymer is widely produced in industry. Since, however,it contains unsaturated bonds in the structure of the main chain, thereare problems in terms of weather resistance, oxidation resistance, heatresistance and the like. In order to dissolve these problems, it iswidely carried out to saturate the structure of the main chain byhydrogenation of the polymer.

In the hydrogenation step after metathesis polymerization of themonomer, in order to prevent the hydrogenation catalyst from activityreduction caused by impurities, it is a common practice to extract andremove the metathesis polymerization catalyst by adding an inactivatingagent for this catalyst to the solution in which the hydrogenation is tobe carried out (Japanese Patent Application Kokai No. 1-311120).However, it is also known a method of obtaining the hydrogenated productof the metathesis polymer by directly adding the hydrogenation catalystwithout removing the metathesis polymerization catalyst from themetathesis polymerization solution and then contacting the solution withhydrogen (as disclosed, for example, in Japanese Patent ApplicationKokai No. 1-138257, No. 1-311120, No. 2-286712, No. 4-93321, etc.). Ofsuch the hydrogenation methods, only one specific example in which ahighly active supported-type catalyst is used as the hydrogenationcatalyst, is known (Japanese Patent Application Kokai No. 2-286712).

The supported-type hydrogenation catalyst is superior in productionefficiency in that it is so highly active that hydrogenation is attainedin a short time, and also that this catalyst is easily removable. Thiscatalyst is therefore widely used. However, both high temperature andhigh pressure are necessary to carry out this hydrogenation. Andbesides, since this catalyst is a lump in which the catalyst componenthas been supported on the carrier, its sufficient dispersion in thepolymer solution is difficult, and therefore this catalyst needs to beadded in large amounts. Because of this, there is a problem of costingtoo much in industrial production. Further, both high temperature andhigh pressure are necessary, so that decomposition and gelation of thepolymer are easy to occur, which sometimes causes a problem of thequality of polymer.

For removing the metathesis polymerization catalyst, there are a methodof removing the catalyst by washing the polymerization solution with asolution containing an inactivating agent for this catalyst, and amethod of removing the catalyst by changing the catalyst into a solidcatalyst residue and then removing this residue by filtration orcentrifugation. In these methods, however, it is difficult to completelyremove the catalyst residue, and it often occurs that the catalystresidue enters the hydrogenation step. In such a case, it is sometimesobserved that the catalyst residue hydrolyzes at the hydrogenation stepto generate a hydrogen halide, which corrodes the reaction vessel.

Also, in the method in which the polymerization solution is directlysupplied to the hydrogenation step without removing the polymerizationcatalyst itself or its residue, the production process is simplified, sothat there is an advantage of the production efficiency being excellent.However, the polymerization catalyst or its residue is contained in theproduction process, so that there is a problem that a hydrogen halide isgenerated in large amounts and the corrosion of the equipment isremarkable.

The catalyst used in the hydrogenation includes the foregoingsupported-type catalyst and a catalyst in which a transition metalcompound (c) and a reductive metal compound (d) have been combined witheach other. The latter catalyst is easily dispersible in the polymersolution, so that addition of small amounts of it will suffice, and alsoboth high temperature and high pressure are not necessary. Thiscatalyst, therefore, is superior to the supported-type catalyst in thatthe cost is low and the quality of the polymer is stable. The activityof this catalyst varies with combination of the transition metalcompound (c) and reductive metal compound (d). In hydrogenation of themetathesis polymer, however, the highly active supported-type catalystis present, so that the combination giving a high activity is notsufficiently investigated about the combined catalyst. The knowncombined catalyst is normally low in the activity as compared with thesupported-type catalyst, and has problems that it takes much time tocomplete the hydrogenation, and the effects of impurities on hindranceto the reaction and reduction of the activity are large. Because ofthis, even if a method itself is known, as described above, in whichhydrogenation is carried out without isolating the polymer from themetathesis polymerization solution, nothing concrete is known about amethod of using the catalyst in which the transition metal compound (c)and reductive metal compound (d) have been combined with each other.Therefore, it has been considered that the metathesis polymer cannot behydrogenated with a good efficiency in the presence of the metathesispolymerization catalyst whether the catalyst has been inactivated ornot.

SUMMARY OF THE INVENTION

The present inventors have made an extensive study on a method forhydrogenating the metathesis polymer with excellent productionefficiency, and as a result have found that even if the metathesispolymer contains the non-inactivated metathesis polymerization catalystcomprising (a) the catalyst component of a transition metal compound and(b) the co-catalyst component of a metal compound, the metathesispolymer can be hydrogenated with a good efficiency using the combinedcatalyst of the transition metal compound (c) with the reductive metalcompound (d), particularly, using the combined catalyst having highactivity, and on the other hand, that the activity of the combinedcatalyst of the transition metal compound (c) with the reductive metalcompound (d) reduces when the inactivating agent for the metathesispolymerization catalyst is added. The present inventors thus completedthe present invention.

Further, the present inventors have made an extensive study with theobject of developing a method for hydrogenating the ring-opened polymerof a cyclo-olefin monomer which generates no hydrogen halide even if thehalogen compound of the transition metal is used in the metathesispolymerization catalyst. As a result, they have found that generation ofa hydrogen halide can be inhibited by allowing an acid-binding compoundto exist at the time of hydrogenation. The present inventors thuscompleted the present invention.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, there is provided a method forhydrogenation of a metathesis polymer characterized in that a metathesispolymer solution obtained by polymerization in the presence of ametathesis polymerization catalyst comprising (a) the catalyst componentof a transition metal compound and (b) the co-catalyst component of ametal compound is brought into contact with hydrogen in the presence ofa hydrogenation catalyst comprising a transition metal compound (c) anda reductive metal compound (d) without substantially inactivating themetathesis polymerization catalyst.

Further, according to the present invention, there is provided a methodfor producing the hydrogenated product of a cycloolefin ring-openedpolymer by bringing a polymer solution, which is obtained byring-opening polymerization of a cycloolefin monomer using a metathesispolymerization catalyst comprising the halide of a transition metal andan organometal compound, into contact with hydrogen in the presence of ahydrogenation catalyst, said method being characterized in that anacid-binding compound is allowed to exist in the hydrogenation systemtogether with the hydrogenation catalyst.

Monomer:

In the present invention, the monomer used to produce the metathesispolymer includes, for example, monocyclic cycloolefins such ascyclobutene, 1-methylcyclobutene, 3-methylcyclobutene,3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene,5,6-dihydrocyclopentadiene, cyclohexene, 4-ethylcyclohexene,cyclooctene, 1-methylcyclooctene, 5-methylcyclooctene,cyclooctatetraene, 1,5-cyclooctadiene, cyclododecene, etc.; polycycliccycloolefins such as bicyclo[3.2.0]-heptene, bicyclo[4.2.01octene,tetrahydroindene, norbornene, norbornadiene, etc.; acetylenes such asacetylene and substituted acetylenes (e.g. propyne, 1-butyne); anddienes having double bonds at the both ends such as 1,6-heptadiene, etc.

Specific examples of the cycloolefin monomer used in the presentinvention include, for example, the following:

1. The above norbornene, the alkyl-, alkylidene-or aromaticgroup-substituted derivatives of the norbornene and the halogen- orpolar group-substituted products of these substituted or non-substitutednorbornene monomers (the polar group includes ester, alkoxy, cyano,amide, imide, silyl, etc.). These compounds include, for example,2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene,5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene,5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene,5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene,5,6-diethoxycarbonyl-2-norbornene,1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene, etc.

2. Monomers in which one or more cyclopentadienes have added tonorbornene, and the same derivatives and substituted products as aboveobtained from the monomers. These compounds include, for example,1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-ethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-ethylidene-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6,6-dimethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,6-methyl-6-methoxycarbonyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene,4,9:5,8-dimethano-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H-benzoindene, etc.

3. Monomers having a polycyclic structure which are the multimer ofcyclopentadiene, and the same derivatives and substituted products asabove obtained from the monomers. These compounds include, for example,dicyclopentadiene, 2,3-dihydrodicyclopentadiene,4,9:5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene, etc.

4. Addition products of cyclopentadiene with tetrahydroindene, etc., andthe same derivatives and substituted products as above obtained from theaddition products. These compounds include, for example,1,4-methano-1,4,4a,4b,5,8,8a,9a-octahydro-9H-fluorene,5,8-methano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene,1,4:5,8-dimethano-1,2,3,4,4a,4b,7,8,8a,9a-decahydro-9H-fluorene,1,4-methano-1,4,4a,9a-tetrahydrofluorene, etc.

These monomers may be used alone or in combination of two or more ofthem.

For the purpose of regulation of the molecular weight, etc., acyclicolefins, preferably α-olefins (e.g. ethylene, propylene, 1-butene,isobutene, styrene, 1-hexene, 4-methylpentene, etc.) may be used as acomonomer in an amount, usually, up to 10 mole%.

Metathesis polymerization catalyst:

The metathesis polymerization catalyst used in the present invention isknown, for example, as disclosed in Japanese Patent Application KokokuNo. 41-20111, Japanese Patent Application Kokai No. 46-14910, JapanesePatent Application Kokoku No. 57-17883 and No. 57-61044, and JapanesePatent Application Kokai No. 54-86600, No. 58-127728 and No. 1-240517.Usually, this catalyst consists substantially of (a) the catalystcomponent of a transition metal compound and (b) the co-catalystcomponent of a metal compound.

The catalyst component of a transition metal compound (a) used in themetathesis polymerization catalyst is the compound of transition metalsbelonging to Groups IVB, VB, VIB, VIIB or VIII of Deming's periodictable. This compound includes the halide, oxyhalide, alkoxyhalide,alkoxide, carboxylate, (oxy)acetylacetonate, carbonyl complex,acetonitrile complex, hydride complex of these transition metals, theirderivatives, and complexes of these compounds or their derivatives witha complexing agent such as P(C₆ H₅)₅, etc.

Specific examples include TiCl₄, TiBr₄, VOCl₃, VOBr₃, WBr₄, WBr₆, WCl₂,WCl₄, WCl₅, WCl₆, WF₄, WI₂, WOBr₄, WOCl₄, WOF₄, MoBr₂, MoBr₃, MoBr₄,MoCl₄, MoCl₅, MoF₄, MoOCl₄, MoOF₄, WO₂, H₂ WO₄, NaWO₄, K₂ WO₄, (NH₄)₂WO₄, CaWO₄, CuWO₄, MgWO₄, (CO)₅ WC (OCH₃)(CH₃), (CO)₅ WC (OC₂ H₅)(CH₃),(CO)₅ WC(OC₂ H₅)(C₄ H₅), (CO)₅ MoC (OC₂ H₅)(CH₃), (CO)₅ Mo=C (C₂ H₅),(N(C₂ H₅)₂), tridecylammonium molybdate, tridecylammonium tungstate,etc. Practically, the compound of W, Mo, Ti or V, particularly thehalide, oxyhalide or alkoxyhalide of these metals is preferred in termsof polymerization activity.

The co-catalyst component of a metal compound (b) used in the metathesispolymerization catalyst is the compound of metals belonging to Groups,IA, IIA, IIB, IIIA or IVA of Deming's periodic table, which compoundneeds to have at least one metal element-carbon bond or metalelement-hydrogen bond. Such the compound includes, for example, theorganic compound of Al, Sn, Li, Na, Mg, Zn, Cd, B, etc. Specifically,there are given organoaluminum compounds such as trimethylaluminum,triethylaluminum, tri-n-propylaluminum, triisopropylaluminum,triisobutylaluminum, trihexylaluminum, trioctylaluminum,triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride,di-n-propylaluminum monochloride, diisobutylaluminum monochloride,di-n-butylaluminum monochloride, diethylaluminum monobromide,diethylaluminum monoiodide, diethylaluminum monohydride,di-n-propylaluminum monohydride, diisobutylaluminum monohydride,methylaluminum sesquichloride, ethylaluminum sesquibromide,isobutylaluminum sesquibromide, ethylaluminum dichloride, ethylaluminumdibromide, propylaluminum dichloride, isobutylaluminum dichloride,ethylaluminum dibromide, ethylaluminum diiodide, etc.; organotincompounds such as tetramethyltin, diethyldimethyltin, tetraethyltin,dibutyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin,triethyltin fluoride, triethyltin chloride, triethyltin bromide,triethyltin iodide, diethyltin difluoride, diethyltin diiodide, ethyltintrifluoride, ethyltin trichloride, ethyltin tribromide, ethyltintriiodide, etc.; organolithium compounds such as n-butyllithium, etc.;organosodium compounds such as n-pentylsodium, etc.; organomagnesiumcompounds such as methylmagnesium iodide, ethylmagnesium bromide,methylmagnesium bromide, n-propylmagnesium chloride, tert-butylmagnesiumchloride, allylmagnesium chloride, etc.; organozinc compounds such asdiethylzinc, etc.; organocadmium compounds such as diethylcadmium, etc.;organoboron compounds such as trimethylboron, triethylboron,tri-n-butylboron, etc.; and the like.

The metathesis polymerization activity can be enhanced by adding a thirdcomponent besides the components (a) and (b). Such the third componentincludes aliphatic tertiary amines, aromatic tertiary amines,molecule-form oxygen, alcohols, ethers, peroxides, carboxylic acids,acid anhydrides, acid chlorides, esters, ketones, nitrogen-containingcompounds, sulfur-containing compounds, halogen-containing compounds,molecule-form iodine, other Lewis acids and the like. Of thesecompounds, aliphatic or aromatic tertiary amines are preferred. Specificexamples of these amines include triethylamine, dimethylaniline,tri-n-butylamine, pyridine, α-picoline and the like. Also, whencompounds having an OH group such as alcohols, etc. are added in amountsexceeding their stoichiometric amount, they function as an inactivatingagent disturbing the metathesis polymerization activity. The alcohols,therefore, need to be added in amounts not exceeding theirstoichiometric amount. The stoichiometric amount referred to hereinmeans a mole number represented by a numerical value obtained bydividing the product of mole number of the component (a) and oxidationnumber of the transition metal contained in the component (a) by thenumber of OH groups per one molecule of the OH group-containingcompound.

As to the relation between the amounts of these components, the ratio ofamounts of the components (a) and (b) is 1:1 to 1:100, preferably 1:2 to1:50 in terms of the molar ratio of the metal elements contained in thecomponents, and that of amounts of the component (a) and third componentis usually 1:0.005 to 1:10, preferably 1:0.05 to 1:3 in terms of themolar ratio of the both components. When the amount of the component (b)is too small relative to that of the component (a), a sufficientactivity expectable from the amount of the component (a) can not beobtained. When the amount of the component (b) is too large, removal ofthe excess component (b) becomes difficult, which raises the cost. Whenthe amount of the third component is too small relative to that of thecomponent (a), the effect of addition of the third component is small,and when the amount of the third component is too large, removal of theexcess third component becomes difficult, which raises the cost.

Metathesis polymerization:

In the present invention, metathesis polymerization can be carried outwithout a solvent, but it can be carried out even in an inert organicsolvent. For example, polymerization of the norbornene monomer isgenerally carried out in an inert organic solvent. Specific examples ofsuch the solvent include aromatic hydrocarbons such as benzene, toluene,xylene, etc.; alicyclic hydrocarbons such as cyclohexane, etc.;halogenated hydrocarbons such as methylene dichloride, dichloroethane,dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene,trichlorobenzene, etc.; ethers such as diethyl ether, etc.; and thelike. These solvents may be used in mixture of two or more of them. Theamount of the solvent is in the range of usually 1 to 100 times,preferably 2 to 20 times in terms of a weight ratio to the amount of themonomer. When the amount of the solvent is too small, the viscosity ofthe polymerization solution becomes high with the progress of thepolymerization, so that it is difficult to obtain a polymer having ahigh polymerization degree. When the amount of the solvent is too large,the catalyst and monomer become difficult to contact with each other, sothat the reaction rate becomes slow and efficiency becomes bad.

The amount of the metathesis polymerization catalyst is in the range ofusually 0.000001 to 1 time, preferably 0.0001 to 0.5 time in terms ofthe molar ratio of amount of the component (a) contained in the catalystto amount of the monomer. Whether the amount of the component (a) is toosmall or too large, the monomer and catalyst become difficult to contactwith each other, so that the reaction rate becomes slow and efficiencybecomes bad.

The molecular weight of the resulting metathesis polymer can beregulated by adding to the reaction solution a compound having at leastC--C double bond or C--C triple bond in the molecule or a polar allylcompound. The former compound includes α-olefins, α,ω-diolefins,acetylenes, etc., and the latter compound includes allyl chloride, allylacetate, trimethylallyloxysilane, etc.

The temperature condition for metathesis polymerization is not critical,but it is usually -20° C. to 100° C., preferably 10° to 50° C., morepreferably 20° C. to 50° C. When the temperature is too low, thereaction rate lowers, and when it is too high, the reaction becomesdifficult to control and energy cost becomes high.

The metathesis polymerization is carried out under a pressure of usually0.1 to 50 kgf/cm², preferably 0.5 to 10 kgf/cm², more preferably 1 to 5kgf/cm².

Metathesis polymer:

The metathesis polymer used in the present invention may be any of ahomopolymer and copolymer, so far as it is a polymer produced with themetathesis polymerization catalyst. And the copolymer may be any of arandom copolymer, block copolymer and graft copolymer. Also, themetathesis polymer used in the present invention needs to have a weightaverage molecular weight of usually 1,000 to 1,000,000, preferably 5,000to 200,000 as measured by GPC. Metathesis polymer solution containingmetathesis polymerization catalyst:

In the present invention, the metathesis polymer solution obtained bypolymerization in the presence of the metathesis polymerization catalystis hydrogenated by contacting it with hydrogen in the presence of thehydrogenation catalyst without inactivating the metathesispolymerization catalyst before hydrogenation. Therefore, theinactivation step can be omitted and production efficiency is good. Whenthe metathesis polymer solution is supplied to the hydrogenation stepafter a large amount of the inactivating agent (e.g. a compound havingan OH group such as water, alcohols, etc.) is added according to theconventional method, the activity of the hydrogenation catalyst largelylowers. Even if the metathesis polymer is once isolated by coagulation,re-dissolved in the solvent and then supplied to the hydrogenation step,the activity of the hydrogenation catalyst is insufficient. However, ifthe metathesis polymerization catalyst is not substantially inactivatedand therefore the unreacted inactivating agent is not present in thesystem, the activity of the hydrogenation catalyst is sufficient.

The concentration of this polymer solution is preferably 1 to 50 wt. %,more preferably 5 to 30 wt. %. When the concentration is too high, itmay be diluted to a desirable one by adding additional inert organicsolvent.

Hydrogenation catalyst:

The hydrogenation catalyst used in the present invention comprises atransition metal compound (c) and reductive metal compound (d). Thiscatalyst is known, for example, as disclosed in Japanese PatentApplication Kokai No. 58-43412, No. 60-26024, No. 64-24826 and No.1-138257.

In the present invention, the transition metal compound (c) used in thehydrogenation catalyst is the compound of transition metals belonging toeither of Groups I or IV to VIII of Deming's periodic table.Specifically, there are given, for example, the compound of transitionmetals such as V, Ti, Cr, Mo, Zr, Fe, Mn, Co, Ni, Pd, Ru, etc., and thecompound includes halides, alkoxides, acetylacetonates, sulfonates,carboxylates, naphthenates, trifluoroacetates and stearates of thesemetals. Specific examples of the compound include tetraisopropoxytitanate, tetrabutoxy titanate, titanocene dichloride, zirconocenedichloride, vanadocene dichloride, triethyl vanadate, tributyl vanadate,chromium(III) acetylacetonate, molybdenyl acetylacetonate,manganese(III) acetylacetonate, iron(III) acetylacetonate, cobalt(III)acetylacetonate, bis(triphenylphosphine)cobalt dichloride, nickel(II)acetylacetonate, bis(tributylphosphine)nickel dichloride,bis(tributylphosphine)palladium dichloride,bis(cyclopentadienyl)titanium dichloride and the like.

In the present invention, the reductive metal compound (d) used in thehydrogenation catalyst is specifically the compound of metals belongingto Groups IA, IIA, IIB, IIIA or IVA of Deming's periodic table, whichcompound needs to have at least one metal atom-carbon bond or metalatom-hydrogen bond. Specifically, there are given aluminum compoundssuch as trimethylaluminum, triethylaluminum, triisobutylaluminum,triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride,methylaluminum sesquichloride, ethylaluminum sesquichloride,diethylaluminum hydride, diisobutylaluminum hydride, etc.; lithiumcompounds such as methyllithium, ethyllithium, n-propyllithium,n-butyllithium, sec-butyllithium, isobutyllithium, n-hexyllithium,phenyllithium, p-tolyllithium, xylyllithium, etc.; zinc compounds suchas diethylzinc, bis(cyclopentadienyl)zinc, diphenylzinc, etc.; magnesiumcompounds such as dimethylmagnesium, diethylmagnesium, methylmagnesiumbromide, methylmagnesium chloride, ethylmagnesium bromide,ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesiumchloride, etc.; and the like. Compounds containing two or more kinds ofreductive metal such as lithiumaluminum hydride, etc. can also be used.

One of specific combined catalysts is those in which the component (c)which is the organometal compound, halide, alkoxide, acetylacetonate,sulfonate or naphthenate of V, Ti, Mn, Fe, Co or Ni, and the component(d) which is the organic compound or hydride of Al, Li, Zn or Mg havebeen combined with each other. These catalysts are preferred becausethey have high activity and undergo only a little effect of impuritieson hindrance to the reaction and reduction of the activity. And, theother of specific combined catalysts is those in which the component (c)which is the organometal compound, halide, alkoxide or acetylacetonateof Ti, Fe, Co or Ni, and the component (d) which is alkylaluminum oralkyllithium have been combined with each other. These catalysts aremore preferred because they have particularly a high activity andundergo only particularly a little effect of impurities on hindrance tothe reaction and reduction of the activity.

As to the relation between the amounts of these components, the amountsof the components (c) and (d) is 1:0.5 to 1:50, preferably 1:1 to 1:8 interms of the molar ratio of metal atoms contained in the components.Whether the amount of the component (d) is too large or too smallrelative to that of the component (c), the hydrogenation activitybecomes insufficient. Particularly, when the amount is too large,gelation and side reaction sometimes occur.

The unsaturated bond in the main chain structure of the polymer ishydrogenated by these hydrogenation catalysts to turn saturated bond,but usually, unsaturated bonds other than those in the main chainstructure are also hydrogenated and saturated. However, when the polymercontains an aromatic ring, unsaturated bonds in this ring can be leftunsaturated without being hydrogenated, for example, by using ahydrogenation catalyst in which bis(cyclopentadienyl)titanium dichloridewhich is the component (c) and alkyllithium which is the component (d)have been combined with each other (Japanese Patent Application KokokuNo. 63-4841), a hydrogenation catalyst in whichdialkyl-bis(cyclopentadienyl)titanium which is the component (c) and areductive magnesium compound which is the component (d) have beencombined with each other (Japanese Patent Application Kokai No.61-28507), or a hydrogenation catalyst in whichdialkyl-bis(cyclopentadienyl)titanium which is the component (c) andalkoxylithiumwhich is the component (d) have been combined with eachother (Japanese Patent Application Kokai No. 1-275605).

Acid-binding compound:

When the catalyst component of a transition metal compound (a)constituting the metathesis polymerization catalyst is a transitionmetal halide such as TiCl₄, WCl₆, etc., or the transition metal compound(c) constituting the hydrogenation catalyst is a transition metal halidesuch as bis(tributylphosphine)nickel dichloride, etc., or the reductivemetal compound (d) is a metal halide such as ethylaluminum dichloride,etc., it sometimes occurs that water is generated at the time ofhydrogenation, these metal halides are hydrolyzed by this water toevolve a hydrogen halide and as a result the hydrogenation reactor iscorroded.

In the present invention, it is desirable to inhibit corrosion of thehydrogenation reactor, etc. by reacting the hydrogen halide with anacid-binding compound.

The acid-binding compound is a compound reacting with a hydrogen halide,and its specific examples include epoxy compounds such as ethyleneoxide, propylene oxide, butylene oxide, cyclohexene oxide, styreneoxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidylether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, epoxyresins, etc.; basic compounds such as calcium hydroxide, magnesiumhydroxide, calcium oxide, magnesium oxide, etc.; powdery, granular orribbon-formmetals such as magnesium, aluminum, zinc, iron, etc.; and thelike. Of these acid-binding compounds, epoxy compounds are preferred interms of their high preventing effect on corrosion of the hydrogenationreactor.

The time at which the acid-binding compound is added may be any timebefore and after addition of the hydrogenation catalyst, so far as it isa time after finish of the polymerization and before beginning of thehydrogenation.

When the acid-binding compound is used, its amount used is 0.5equivalent or more, preferably 1 to 100 equivalents, more preferably 2to 10 equivalents based on the stoichiometric amount of an acidgenerated by hydrolysis of the metathesis polymerization catalyst andhydrogenation catalyst, in other words, the mole amount of the halogenatom contained in the metathesis polymerization catalyst andhydrogenation catalyst. For example, when the metathesis polymerizationcatalyst comprising WCl₆ and triethylaluminum is used, a hydrogen halideis not generated from triethylaluminum, but hydrogen chloride can begenerated in amounts up to a maximum of 6 moles based on 1 mole of WCl₆.When the acid-binding compound used is aluminum which turns trivalentmetal ion, in order to inhibit corrosion of the hydrogenation reactor bya hydrogen halide generated from WCl₆, the amount of the acid-bindingcompound used is 1 mole (=6 moles +3×0.5), preferably 2 to 200 moles,more preferably 4 to 20 moles based on 1 mole of WCl₆. Similarly, thesame proportion of the acid-binding compound as above is used to preventthe reaction reactor from corrosion by an acid generated by hydrolysisof the hydrogenation catalyst.

When hydrogenation is carried out using the so-called homogeneouscatalyst in which the transition metal compound (c) and reductive metalcompound (d) have been combined with each other, as in the presentinvention, the generated water reacts with the reductive metal compound(d), so that, usually, the hydrogenation reactor, etc. are not corrodedat the time of hydrogenation. However, after the hydrogenation isfinished, that is, after the reaction solution in the reactor iscontacted with oxygen in air by the after-treatment of hydrogenation inwhich the hydrogenation is stopped and the hydrogen gas in the reactoris replaced by air, the reaction product of the reductive metal compoundwith water is oxidized into water again to generate a hydrogen halide.It is preferred, therefore, to add the acid-binding compound beforefinish of the hydrogenation, that is, before contact of the reactionsolution with air.

Hydorgenation:

The amount of the hydrogenation catalyst added to the metathesis polymersolution containing the metathesis polymerization catalyst is usually0,001 to 1000 mmoles, preferably 0.1 to 100 mmoles, in terms of theamount of the transition metal compound, based on 100 g of the polymer.Addition of excess catalyst costs high, and besides after-treatment suchas catalyst removal after hydrogenation is difficult.

The hydrogenation is carried out by introducing hydrogen into thepolymer solution, and for example, a method of sufficiently contactingthe introduced hydrogen with the polymer while stirring the solution, ispreferred. The hydrogen pressure used in the hydrogenation is usually0.1 to 100 kg/cm², preferably 2 to 40 kg/cm². When the pressure is toolow, the hydrogenation does not proceed, and when it is too high, thereaction becomes difficult to control, and also side reaction andgelation are caused.

In the present invention, the hydrogenation is carried out at usually 0°to 200° C., preferably 20° C. to 100° C. When the temperature is toolow, the hydrogenation rate is slow, and when it is too high,decomposition and gelation of the polymer are easy to occur, and alsoenergy cost becomes high.

The hydrogenation can be stopped by stopping supply of hydrogen. It maybe stopped by adding a compound having an OH group (e.g. water,alcohols) to inactivate the hydrogenation catalyst.

Recovery and purification of hydrogenated product:

A method for recovering the hydrogenated product of the polymer from thehydrogenation solution is not critical. For example, it will suffice tocoagulate the hydrogenated product of the polymer by adding a largeamount of a poor solvent (e.g. an alcohol) to the hydrogenationsolution.

Hydrogenated product:

In the hydrogenated product obtained by the method of the presentinvention, the unsaturated bond in the main chain structure of thepolymer has been saturated. The hydrogenation rate varies with the kindand amount of the hydrogenation catalyst, hydrogenation temperature,hydrogen pressure and the like. A desirable hydrogenation rate varieswith the object of hydrogenation. Generally, however, the rate ofhydrogenation of the unsaturated bond in the main chain structure ispreferably 50% or more, more preferably 90% or more, particularlypreferably 99% or more. Generally, when the rate of hydrogenation of theunsaturated bond in the main chain structure is low, the heat resistanceand light fastness become poor.

Unsaturated bonds other than those in the main chain structure also aregenerally hydrogenated at the same rate as in the main chain structure.However, unsaturated bonds in an aromatic ring, as described before, canbe left unsaturated without being selectively hydrogenated by selectingthe hydrogenation catalyst. The hydrogenation rate of the unsaturatedbonds in the aromatic ring and that of other unsaturated bonds can bemeasured in distinction from each other by infrared absorption spectrum.

The hydrogenated product of the metathesis polymer obtained by thepresent invention is useful in a wide field as various kinds of moldedarticle, including optical materials. For example, there are givenoptical materials (optical discs, optical lenses, prisms,light-diffusing plates, optical cards, optical fibers, optical mirrors,substrates for liquid crystal display elements, light-conducting plates,polarizing films, phase retarder films, etc.), medical materials (e.g.,containers for liquid, powdery or solid medicines such as containersholding liquid medicines for injection, ampoules, vials, pre-filledsyringes, bags for transfusion, sealed medicine bags, press throughpackages, containers for solid medicines, containers for eye lotions,etc.; food containers; sampling containers such as sampling test tubesfor blood test, caps for medicine containers, blood-collecting tubes,test sample containers, etc., sterilizing apparatus for medical toolssuch as injectors, surgical knives, forceps, gauzes, contact lenses,etc.; experimental and analytical tools such as beakers, Petri dishes,flasks, test tubes, centrifugal tubes, etc.; optical parts for medicaltreatment such as plastic lenses for medical test, etc.; pipingmaterials such as transfusion tubes for medical treatment, pipes,joints, valves, etc.; artificial organs and parts such as dental plates,artificial hearts, artificial dental roots, etc.; and the like);materials for treatment of electronic parts (e.g., containers fortreatment and transportation such as tanks, trays, carriers, cases,etc.; protecting materials such as carrier tapes, separation films,etc.; pipings such pipes, tubes, valves, flowmeters, filters, pumps,etc.; liquid-holding containers such as sampling containers, bottles,ampoule bags, etc.; and the like); general insulating materials (e.g.,covering materials for electric wires and cables, insulating materialsfor electronic instruments for public welfare and industry, meters,instruments such as copying machines, computers, printers, televisions,video-cameras etc.), etc.; circuit boards (e.g., hard printed circuitboards, flexible printed circuit boards, multilayer printed circuitboards, etc., particularly high-frequency circuit boards for satellitecommunication instruments required for high-frequency characteristics);materials for transparent and conductive films (e.g., liquid crystalsubstrates, optical memories, flat-surface heaters such as defrostersfor cars and airplanes, etc.), sealing materials for electro-conductors(e.g., transistors, IC, LSI, LED, etc.) and parts therefor, sealingmaterials for electric and electronic parts (e.g., motors, condensers,switches, sensors, etc.), structural materials for parabola antennas,flat antennas and radar domes; and the like.

Working examples;

The present invention will be illustrated specifically with reference tothe following referential examples, examples and comparative examples.

REFERENTIAL EXAMPLE 1

One hundred and fifty parts by weight of dicyclopentadiene was dissolvedin 300 parts by weight of cyclohexane, and 1 part by weight of 1-hexenewas added as a molecular weight-regulating agent. To this solution wereadded as the component (a) 30 parts by weight of a 0.8% cyclohexanesolution of tungsten hexachloride, as the component (b) 4 parts byweight of a 10% cyclohexane solution of tetrabutyltin and as the thirdcomponent 0.8 part by weight of dibutyl ether. Metathesis ring-openingpolymerization was carried out at 70° C. for 1 hour with stirring toobtain a polymer solution. The polymerization conversion was 100%, andthe weight average molecular weight of the polymer measured by GPC was23,300.

Referential Example 2

The polymer solution was obtained in the same manner as in ReferentialExample 1 except that 105 parts by weight of dicyclopentadiene and 45parts by weight of norbornene were used in place of 150 parts by weightof dicyclopentadiene. The polymerization conversion was 100%, and theweight average molecular weight of the polymer was 30,500.

Referential Example 3

The polymer solution was obtained in the same manner as in ReferentialExample 1 except that tetraphenyltin was used in place of tetrabutyltin.The polymerization conversion was 100%, and the weight average molecularweight of the polymer was 23,900.

Referential Example 4

The polymer solution was obtained in the same manner as in ReferentialExample 1 except that norbornene was used in place of dicyclopentadieneand tetramethyltin was used in place of tetrabutyltin. Thepolymerization conversion was 100%, and the weight average molecularweight of the polymer was 27,000.

Referential Example 5

One hundred parts by weight of tetrahydroindene was dissolved in 244parts by weight of cyclohexane. To this solution were added as thecomponent (a) 54 parts by weight of a 0.8% cyclohexane solution oftungsten hexachloride, as the component (b) 1.8 parts by weight of a 23%cyclohexane solution of ethylaluminum dichloride and as the thirdcomponent 0.055 part by weight of ethyl alcohol. Metathesispolymerization was carried out at 25° C. for 1 hour with stirring toobtain a polymer solution. The polymerization conversion was 38%, andthe weight average molecular weight of the polymer measured by GPC was76,200.

Referential Example 6

One hundred parts by weight of 8-methyltetracyclododecene was dissolvedin 250 parts by weight of cyclohexane, and 0.5 part by weight of1-hexene was added as a molecular weight-regulating agent. To thissolution were added as the component (a) 1.6 parts by weight of titaniumtetrachloride, as the component (b) 11 parts by weight of a 15%cyclohexane solution of triethylaluminum and as the third component 3.4parts by weight of triethylamine. Metathesis ring-opening polymerizationwas carried out at 40° C. for 1 hour with stirring to obtain a polymersolution. The polymerization conversion was 85%, and the weight averagemolecular weight of the polymer measured by GPC was 34,800.

Example 1

To a 2-liter autoclave equipped with a stirrer were added 100 g of thepolymer solution obtained in Referential Example 1, 0.38 g ofcobalt(III) acetylacetonate as the component (c) and 300 g ofcyclohexane. After replacing the air in the autoclave by hydrogen, asolution of 0.84 g of triisobutylaluminum, the component (d), in 9.16 gof cyclohexane was added to the autoclave. Reaction was carried out at80° C. for 1 hour under a hydrogen pressure of 10 kg/cm². At a pointwhen thirty minutes elapsed after beginning of the reaction, it wasobserved that hydrogen absorption had been completed. The hydrogenationrate of the polymer was 98.9%.

Example 2

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 2 was used in placeof the polymer solution obtained in Referential Example 1, and that asolution of 1.68 g of triisobutylaluminum, the component (d), in 8.32 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.4%.

Example 3

Reaction was carried out in the same manner as in Example 1 except that1.90 g of cobalt(III) acetylacetonate was used as the component (c), asolution of 4.20 g of triisobutylaluminum, the component (d), in 5.80 gof cyclohexane was used, and that the reaction temperature was 60° C. Ata point when thirty minutes elapsed after beginning of the reaction, itwas observed that hydrogen absorption had been completed. Thehydrogenation rate of the polymer was 99.9%.

Example 4

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 6 was used in placeof the polymer solution obtained in Referential Example 1, 1.90 g ofcobalt(III) acetylacetonate was used as the component (c), a solution of4.20 g of triisobutylaluminum, the component (d), in 5.80 g ofcyclohexane was used, and that the reaction temperature was 60° C. At apoint when thirty minutes elapsed after beginning of the reaction, itwas observed that hydrogen absorption had been completed. Thehydrogenation rate of the polymer was 99.9%.

Example 5

Reaction was carried out in the same manner as in Example 1 except that0.14 g of nickel(II) acetylacetonate was used as the component (c), anda solution of 0.42 g of triisobutylaluminum, the component (d), in 9.58g of cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.9%.

Example 6

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 2 was used in placeof the polymer solution obtained in Referential Example 1, 0.14 g ofnickel(II) acetylacetonate was used as the component (c), and that asolution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.9%.

Example 7

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 5 was used in placeof the polymer solution obtained in Referential Example 1, 0.14 g ofnickel(II) acetylacetonate was used as the component (c), and that asolution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.9%.

Example 8

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 4 was used in placeof the polymer solution obtained in Referential Example 1, 0.14 g ofnickel(II) acetylacetonate was used as the component (c), and that asolution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.9%.

Example 9

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 2 was used in placeof the polymer solution obtained in Referential Example 1, 0.25 g ofbis(cyclopentadienyl)titanium dichloride was used as the component (c),and that a solution of 0.26 g of n-butyllithium, the component (d), in9.74 g of cyclohexane was used. At a point when thirty minutes elapsedafter beginning of the reaction, it was observed that hydrogenabsorption had been completed. The hydrogenation rate of the polymer was91.5%.

Example 10

Reaction was carried out in the same manner as in Example 1 except that0.25 g of bis(cyclopentadienyl)titanium dichloride was used as thecomponent (c), a solution of 0.26 g of n-butyllithium, the component(d), in 9.74 g of cyclohexane was used, the reaction temperature was 60°C., and that the hydrogen pressure was 30 kgf/cm². At a point whenthirty minutes elapsed after beginning of the reaction, it was observedthat hydrogen absorption had been completed. The hydrogenation rate ofthe polymer was 97.3%.

Example 11

Reaction was carried out in the same manner as in Example 1 except that1.00 g of bis(cyclopentadienyl)titanium dichloride was used as thecomponent (c), a solution of 1.83 g of triethylaluminum, the component(d), in 8.17 g of cyclohexane was used, the reaction temperature was 60°C., and that the hydrogen pressure was 30 kgf/cm². At a point whenthirty minutes elapsed after beginning of the reaction, it was observedthat hydrogen absorption had been completed. The hydrogenation rate ofthe polymer was 93.8%.

Example 12

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 6 was used in placeof the polymer solution obtained in Referential Example 1, 1.00 g ofbis(cyclopentadienyl)titanium dichloride was used as the component (c),and that a solution of 1.02 g of n-butyllithium, the component (d), in8.98 g of cyclohexane was used. At a point when thirty minutes elapsedafter beginning of the reaction, it was observed that hydrogenabsorption had been completed. The hydrogenation rate of the polymer was91.7%.

Example 13

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 2 was used in placeof the polymer solution obtained in Referential Example 1, 0.30 g oftetraisopropoxy titanate was used as the component (c), and that asolution of 0.85 g of triisobuytylaluminum, the component (d), in 9.15 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 97.5%.

Example 14

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 3 was used in placeof the polymer solution obtained in Referential Example 1, 1.51 g oftetraisopropoxy titanate was used as the component (c), and that asolution of 2.43 g of triethylaluminum, the component (d), in 7.57 g ofcyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 92.3%.

Example 15

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Referential Example 2 was used in placeof the polymer solution obtained in Referential Example 1, 1.51 g oftetraisopropoxy titanate was used as the component (c), and that asolution of 1.36 g of n-butyllithium, the component (d), in 8.64 g ofcyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 92.7%.

Example 16

Reaction was carried out in the same manner as in Example 1 except that1.51 g of tetraisopropoxy titanate was used as the component (c), andthat a solution of 2.12 g of triisobutylaluminum, the component (d), in7.88 g of cyclohexane was used. At a point when thirty minutes elapsedafter beginning of the reaction, it was observed that hydrogenabsorption had been completed. The hydrogenation rate of the polymer was95.4%.

Example 17

To a 2-liter autoclave equipped with a stirrer were added 100 g of thepolymer solution obtained in Referential Example 1, 0.3 g of butylglycidyl ether, 0.38 g of cobalt(III) acetylacetonate as the component(c) and 300 g of cyclohexane. After replacing the air in the autoclaveby hydrogen, a solution of 0.84 g of triisobutylaluminum, the component(d), in 9.16 g of cyclohexane was added to the autoclave. Reaction wascarried out at 80° C. for 1 hour under a hydrogen pressure of 10kgf/cm². At a point when thirty minutes elapsed after beginning of thereaction, it was observed that hydrogen absorption had been completed.The hydrogenation rate of the polymer was 98.7%.

Using this autoclave, hydrogenation was repeated ten times in totalunder the same conditions. The inner surface of the autoclave wasexamined, but corrosion was not observed.

Comparative Example 1

Five hundred grams of the polymer solution obtained in ReferentialExample 1 was added dropwise to 20 liters of violently stirredisopropanol to coagulate and precipitate the polymer. The polymer wasfiltered off and sufficiently washed with isopropanol. By thistreatment, the metathesis polymerization catalyst was inactivated andremoved from the polymer. The resulting polymer was dried at 60° C. for3 days under reduced pressure. Thirty grams of the resulting polymer wasdissolved in 370 g of cyclohexane to obtain a polymer solution.

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained above was used in place of the polymersolution obtained in Referential Example 1. At a point when thirtyminutes elapsed after beginning of the reaction, it was observed thathydrogen absorption had been completed. The hydrogenation rate of thepolymer was 97.4%. The hydrogenation rate was higher in Example 1.

Comparative Example 2

Cyclohexane was added to the polymer solution obtained in ReferentialExample 1 to adjust the polymer concentration to 10 wt. %. One hundredgrams of this polymer solution and an adsorbent, prepared byimpregnating 1.0 g of activated clay with 0.5 g of water, were added toa 200-ml flask, and the mixture was stirred at room temperature for 2hours. This treated solution was centrifuged for 30 minutes at 1500 G toremove the adsorbent containing adsorbed metathesis polymerizationcatalyst. Thus, the polymer solution was obtained.

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained above was used in place of the polymersolution obtained in Referential Example 1. At a point when thirtyminutes elapsed after beginning of the reaction, it was observed thathydrogen absorption had been completed. The hydrogenation rate of thepolymer was 70.4%. The hydrogenation rate was higher in Example 1 ascompared with Example 1.

Comparative Example 3

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Comparative Example 3 was used in placeof the polymer solution obtained in Referential Example 1, 1.90 g ofcobalt(III) acetylacetonate was used as the component (c), a solution of4.20 g of triisobutylaluminum, the component (d), in 5.80 g ofcyclohexane was used, and that the reaction temperature was 60° C. At apoint when thirty minutes elapsed after beginning of the reaction, itwas observed that hydrogen absorption had been completed. Thehydrogenation rate of the polymer was 99.7%. The hydrogenation rate washigher in Example 3 as compared with Example 3.

Comparative Example 4

Reaction was carried out in the same manner as in Example 1 except thatthe polymer solution obtained in Comparative Example 1 was used in placeof the polymer solution obtained in Referential Example 1, 0.14 g ofnickel(II) acetylacetonate was used as the component (c), and that asolution of 0.42 g of triisobutylaluminum, the component (d), in 9.58 gof cyclohexane was used. At a point when thirty minutes elapsed afterbeginning of the reaction, it was observed that hydrogen absorption hadbeen completed. The hydrogenation rate of the polymer was 99.7%. Thehydrogenation rate was higher in Example 5 as compared with ComparativeExample 4.

Comparative Example 5

Hydrogenation was repeated ten times in the same autoclave of Example 1in the same manner as in Example 1. The inner surface of the autoclavewas examined to find that minute corrosion was observed near theboundary between the parts of the inner surface with which the reactionsolution contacted and did not contact.

Referential Example 7

Under a nitrogen atmosphere, 300 parts by weight of cyclohexane, 0.48part by weight of 1-hexene and 0.30 part by weight of tetrabutyltin wereadded to 10 parts by weight of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene. Whilekeeping the resulting mixture at 40° C. with stirring, 90 parts byweight of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene and32.0 parts by weight of a 0.5 wt % cyclohexane solution of tungstenhexachloride were continuously added thereto over 60 minutes.Thereafter, reaction was carried out for 1 hour to obtain 424 parts byweight of a ring-opened polymer solution.

This ring-opened polymer solution was analyzed by gas chromatography,and it was found that the residual monomer was not detected, and thatthe conversion to the polymer was nearly 100%.

Referential Example 8

Under a nitrogen atmosphere, 250 parts by weight of cyclohexane, 0.59part by weight of 1-hexene and 0.60 part by weight of tetraoctyltin wereadded to 7.0 parts by weight of dicyclopentadiene and 3.0 parts byweight of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene. Whilekeeping the resulting mixture at 40° C. with stirring, a mixture of 63parts by weight of dicyclopentadiene and 27 parts by weight of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene and39.0 parts by weight of a 0.5 wt. % cyclohexane solution of tungstenhexachloride were continuously added thereto over 60 minutes.Thereafter, reaction was carried out for 1 hour to obtain 382 parts byweight of a ring-opened polymer solution.

This ring-opened polymer solution was analyzed by gas chromatography,and it was found that either of the monomers, cyclopentadiene and6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, wasnot detected, and that the conversion to the polymer was nearly 100%.

Example 18

To 100 parts by weight of the ring-opened polymer solution obtained inReferential Example 7 were added 0.14 part by weight of butyl glycidylether and 0.63 g of a nickel-alumina catalyst (N163A produced by NikkiKagaku Co.). The resulting mixture was added to a pressure-proof reactormade of SUS-316. Hydrogen was introduced into the reactor, andhydrogenation was carried out at 210° C. for 6 hours under a hydrogenpressure of 45 kg/cm². After finish of the reaction, the reactionsolution was diluted with 65 parts by weight of cyclohexane, andcatalyst residues were removed by filtration. Thus, 158 parts by weightof a solution containing the hydrogenated product of the ring-openedpolymer.

Fifty parts by weight of this solution was poured into 150 parts byweight of isopropyl alcohol with stirring to coagulate the hydrogenatedproduct of the ring-opened polymer. This coagulated product wasrecovered by filtration, washed with 100 parts by weight of isopropylalcohol and dried at 120° C. for 40 hours under 1 Torr or less in avacuum drier. Thus, 7.0 parts by weight of the hydrogenated product ofthe ring-opened polymer of6-methyl-l,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

This hydrogenated product had a number average molecular weight of29,000 and a weight average molecular weight of 65,000 as valuesconverted to polystyrene basis by gel.permeation.chromatography, ahydrogenation rate of 99.8% or more measured by ¹ H-NMR spectrum, and aglass transition temperature of 151° C. measured by differentialscanning calorimetry.

Twenty-five grams of this hydrogenated product was burnt to ashes. Theashes were dissolved in sulfuric acid and analyzed by ICP analysis. As aresult, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less and that of the nickelatom was 25 ppb (detection limit) or less.

The above hydrogenation was carried out four times in succession. Afterthe fourth hydrogenation was finished, the inner surface of thepressure-proof reactor was examined, but abnormalities such ascorrosion, etc. were not observed.

Example 19

To 100 parts by weight of the ring-opened polymer solution obtained inReferential Example 7 were added 0.14 part by weight of butyl glycidylether and 0.081 part by weight of isopropyl alcohol, and the resultingmixture was stirred at 50° C. for 4 hours to inactivate thepolymerization catalyst. Thereafter, 0.50 part by weight of anickel-alumina catalyst (N163A) was added to the mixture which was thenadded to the same pressure-proof reactor as used in Example 1. Afterintroducing hydrogen into the reactor, hydrogenation was carried out at210° C. for 6 hours under a hydrogen pressure of 45 kg/cm². After finishof the reaction, the reaction solution was diluted with 65 parts byweight of cyclohexane, and catalyst residues were removed by filtration.Thus, 159 parts by weight of a solution containing the hydrogenatedproduct of the ring-opened polymer.

Fifty parts by weight of this solution was coagulated and dried in thesame manner as in Example 1 to obtain 7.1 parts by weight of thehydrogenated product of the ring-opened polymer of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

The same analyses as in Example 18 were carried out, and it was foundthat this hydrogenated product has a number average molecular weight of29,000 and a weight average molecular weight of 65,000, a hydrogenationrate of 99.8% or more and a glass transition temperature of 151° C.Further, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less and that of the nickelatom was 25 ppb (detection limit) or less.

The above decomposition of the polymerization catalyst and hydrogenationwere carried out four times in succession. After the fourthhydrogenation was finished, the inner surface of the pressure-proofreactor was examined, but abnormalities such as corrosion, etc. were notobserved.

Example 20

To 100 parts by weight of the ring-opened polymer solution obtained inReferential Example 8 were added 0.19 part by weight of butyl glycidylether and 0.11 part by weight of isopropyl alcohol to inactivate thepolymerization catalyst in the same manner as in Example 2. Thereafter,0.57 part by weight of a nickel-alumina catalyst (N163A) was added asthe hydrogenation catalyst to the mixture which was then added to thesame pressure-proof reactor as used in Example 1. After introducinghydrogen into the reactor, hydrogenation was carried out at 210° C. for6 hours under a hydrogen pressure of 45 kg/cm². After finish of thereaction, the reaction solution was diluted with 90 parts by weight ofcyclohexane, and catalyst residues were removed by filtration. Thus, 180parts by weight of a solution containing the hydrogenated product of thering-opened polymer.

Fifty parts by weight of this solution was coagulated and dried in thesame manner as in Example 1 to obtain 7.1 parts by weight of thehydrogenated product of the ring-opened polymer of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

The same analyses as in Example 18 were carried out, and it was foundthat this hydrogenated product had a number average molecular weight of27,000, a weight average molecular weight of 57,000, a hydrogenationrate of 99.8% or more and a glass transition temperature of 105° C.Further, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less and that of the nickelatom was 25 ppb (detection limit) or less.

The same decomposition of the polymerization catalyst and hydrogenationas described above were carried out four times in succession. After thefourth hydrogenation was finished, the inner surface of thepressure-proof reactor was examined, but abnormalities such ascorrosion, etc. were not observed.

Example 21

Inactivation of the polymerization catalyst and hydrogenation werecarried out in the same manner as in Example 19 except that 0.065 partby weight of propylene oxide was used in place of butyl glycidyl ether.Thus, 155 parts by weight of the solution containing the hydrogenatedproduct of the ring-opened polymer was obtained.

Fifty parts by weight of this solution was coagulated and dried in thesame manner as in Example 1 to obtain 6.9 parts by weight of thehydrogenated product of the ring-opened polymer of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

The same analyses as in Example 18 were carried out, and it was foundthat this hydrogenated product had a number average molecular weight of29,000, a weight average molecular weight of 65,000, a hydrogenationrate of 99.8% or more and a glass transition temperature of 151° C.Further, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less and that of the nickelatom was 25 ppb (detection limit) or less.

The same decomposition of the polymerization catalyst and hydrogenationas described above were carried out four times in succession. After thefourth hydrogenation was finished, the inner surface of thepressure-proof reactor was examined, but abnormalities such ascorrosion, etc. were not observed.

Example 22

Inactivation of the polymerization catalyst and hydrogenation werecarried out in the same manner as in Example 19 except that 0.30 part byweight of powdery zinc was used in place of butyl glycidyl ether. Thus,158 parts by weight of the solution containing the hydrogenated productof the ring-opened polymer was obtained.

Fifty parts by weight of this solution was coagulated and dried in thesame manner as in Example 1 to obtain 7.0 parts by weight of thehydrogenated product of the ring-opened polymer of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

The same analyses as in Example 18 were carried out, and it was foundthat this hydrogenated product had a number average molecular weight of29,000, a weight average molecular weight of 65,000, a hydrogenationrate of 99.8% or more and a glass transition temperature of 151° C.Further, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less, that of the nickel atomwas 25 ppb (detection limit) or less and that of the zinc atom was 25ppb (detection limit) or less.

The same decomposition of the polymerization catalyst and hydrogenationas described above were carried out four times in succession. After thefourth hydrogenation was finished, the inner surface of thepressure-proof reactor was examined, but abnormalities such ascorrosion, etc. were not observed.

Comparative Example 6

Hydrogenation was carried out in the same manner as in Example 18 exceptthat butyl glycidyl ether was not used, to obtain 154 parts by weight ofa solution containing the hydrogenated product of the ring-openedpolymer.

Fifty parts by weight of this solution was coagulated and dried in thesame manner as in Example 1 to obtain 7.2 parts by weight of thehydrogenated product of the ring-opened polymer of6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene.

The same analyses as in Example 18 were carried out, and it was foundthat this hydrogenated product had a number average molecular weight of29,000, a weight average molecular weight of 65,000 and a glasstransition temperature of 151° C., but that its hydrogenation rate was98.5%. Further, it was found that the amount of the tungsten atom in thehydrogenated product was 25 ppb (detection limit) or less, that of thetin atom was 25 ppb (detection limit) or less and that of the nickelatom was 25 ppb (detection limit) or less.

The same hydrogenation as described above was carried out four times insuccession. After the fourth hydrogenation was finished, the innersurface of the pressure-proof reactor was examined. As a result, it wasfound that minute corrosion was observed at the upper part of thereactor and near the boundary between the lower and upper parts of theinner surface with which the hydrogenation solution contacted and didnot contact, respectively.

According to the method of the present invention, before the beginningof hydrogenation of the polymer obtained from the monomer, there is noneed to remove the metathesis polymerization catalyst used in thepolymerization of the monomer. Because of this, the hydrogenation can becarried out with a good efficiency and besides in the absence of theinactivating agent for the metathesis polymerization catalyst disturbingthe activity of the hydrogenation catalyst. Therefore, the hydrogenationis easy and provides the hydrogenated product of high hydrogenationrate.

Further, according to the method of the present invention, the innersurface of a hydrogenation reactor can be prevented from corrosion by ahydrogen halide, and besides steps for removing the polymerizationcatalyst and its residues can be omitted, so that this method is veryadvantageous for industrial production.

What is claimed is:
 1. A method for preparing a hydrogenated metathesispolymer which comprises:metathetically polymerizing a monomer in thepresence of a metathesis catalyst comprising (a) a catalyst component ofa transition metal compound and (b) a co-catalyst component of a metalcompound, and, without inactivating the metathesis catalyst,hydrogenating the thus formed metathesis polymer in the presence of ahydrogenation catalyst comprising (c) a transition metal compound and(d) a reductive metal compound.
 2. A method for preparing a hydrogenatedmetathesis polymer which comprises:metathetically polymerizing a monomerin a reaction system containing a metathesis catalyst comprising (a) acatalyst component of a transition metal compound and (b) a co-catalystcomponent of a metal compound, and, without inactivating the metathesiscatalyst, hydrogenating the thus formed metathesis polymer in thepresence of a hydrogenation catalyst comprising (c) a transition metalcompound and (d) a reductive metal compound, adding an acid-bindingcompound to the reaction system, and recovering the hydrogenatedmetathesis polymer from the reaction system.
 3. A method according toclaim 1, wherein the transition metal compound (c) is the organometalcompound, halide, alkoxide, acetylacetonate, sulfonate or naphthenate ofV, ti, Mn, Fe, Co or Ni.
 4. A method according to claim 3, wherein thetransition metal compound (c) is the organometal compound, alkoxide oracetylacetonate of Ti, Fe, Co or Ni.
 5. A method according to claim 1,wherein the reductive metal compound (d) is the organometal compound orhydride of Al, Li, Zn or Mg.
 6. A method according to claim 5, whereinthe reductive metal compound (d) is alkylaluminum or alkyllithium.
 7. Amethod according to claim 1, wherein the catalyst component of atransition metal compound (a) is the halide, oxyhalide or alkoxyhalideof W, Mo, ti or V.
 8. A method according to claim 7, wherein theco-catalyst component of a metal compound (b) is the organic compound ofAl, Sn, Li, Na, Mg, Zn, Cd or B.
 9. A method according to claim 1,wherein the monomer is a monocyclic cycloolefin, polycyclic cycloolefin,acetylenes or dienes having double bonds at the both ends.
 10. A methodaccording to claim 1, wherein metathesis polymerization of the monomeris carried out in an inert organic solvent.
 11. A method according toclaim 10, wherein the inert organic solvent is an aromatic hydrocarbon,alicyclic hydrocarbon, halogenated hydrocarbon and/or an ether.
 12. Amethod according to claim 10, wherein the amount of the inert organicsolvent is 1 to 100 times by weight that of the monomer.
 13. A methodaccording to claim 1, wherein the amount of the catalyst component of atransition metal compound (a) is 0.000001 to 1 time by mole that of themonomer.
 14. A method according to claim 1, wherein the amount of theco-catalyst component of a metal compound (b) is 1 to 100 times that ofthe catalyst component of a transition metal compound (a) in terms ofthe molar ratio of the metal atoms contained in the components (b) and(a).
 15. A method according to claim 1, wherein the amount of thetransition metal compound (c) is 0.001 to 1000 mmoles based on 100 g ofthe metathesis polymer.
 16. A method according to claim 1, wherein theamount of the reductive metal compound (d) is 0.5 to 50 times that ofthe transition metal compound (c) in terms of the molar ratio of themetal atoms contained in the compounds (d) and (c).
 17. A methodaccording to claim 1, wherein the hydrogenation rate of the unsaturatedbond contained in the main chain structure of the metathesis polymer is50% or more.
 18. A method according to claim 2, wherein the acid-bindingcompound is an epoxy compound.
 19. A method according to claim 18,wherein the acid-binding compound is ethylene oxide, propylene oxide,butylene oxide, cyclohexene oxide, styrene oxide, methyl glycidyl ether,ethyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether,ethylene glycol diglycidyl ether or an epoxy resin.